Chemoadaptive Polymeric Assemblies by Integrated Chemical Feedback in Self-Assembled Synthetic Protocells

Abstract

The design and chemical synthesis of artificial material objects which can mimic the functions of living cells is an important ongoing scientific endeavor. A key challenge necessary for fulfilling the criteria for a system to be living currently regards evolution, which is derived from adaptivity. Integrated chemical loops capable of feedback control are required to achieve chemical systems which exhibit adaptivity. To explore this, we present an integrated, two-component orthogonal chemical process involving reversible addition–fragmentation chain transfer (RAFT) based polymerization-induced self-assembly (PISA) and a copper-catalyzed azide–alkyne click (CuAAC) coupling reaction. The chemical processes are linked through electron transfer from the activated chain-transfer agent (CTA) to the dormant Cu(II) precatalyst. We show that combining these complementary chemistries in a single reaction pot resulted in two primary outcomes: (i) simplification of the PISA process to synthesize the macro-CTA in situ from available nonamphiphilic components and (ii) routes to complexity and adaptation involving population dynamics, morphologies, and dissipative phenomena observed during in situ microscopy analysis.

Greatly Enhanced Accessibility and Reproducibility of Worm‐like Micelles by In Situ Crosslinking Polymerization‐Induced Self‐Assembly

“…Case III: Water is an abundant, economical, and green solvent. Therefore, aqueous PISA formulations are very attractive from both the ecological and economic points of view [60–68] . In this case, aqueous PISA formulations in the absence and presence of the water miscible crosslinker tetraethylene glycol dimethacrylate (TEGDMA) were studied (Table S10).…”

“…Therefore, aqueous PISA formulations are very attractive from both the ecological and economic points of view. [60][61][62][63][64][65][66][67][68] In this case, aqueous PISA formulations in the absence and presence of the water miscible crosslinker tetraethylene glycol dimethacrylate (TEGDMA) were studied (Table S10). First, water miscible macro RAFT agent poly(oligo(ethylene glycol) methyl ether methacry-late) (POEGMA 14 -PETTC) was synthesized (Figure S29 and S30).…”

Triggered Polymersome Fusion

“…The use of kinetic control to generate out-of-equilibrium states is being increasingly exploited to endow chemical systems with emergent functions, such as directional motion, − transient assembly, − and concentration gradient formation. − However, the application of this approach to nanoscale systems derived from covalent polymers remains largely unexplored. ,,− Here, we demonstrate that assembled glassy polymers can form an out-of-equilibrium assembly that can be used as a transient store of energy. This would not be possible if polymer assembly occurred under thermodynamic control.…”

Thermodynamic State Machine Network

“…If the massive “parallelism” afforded by an Avogadro’s number of reactants can be configured into interacting “cells”, each with a much smaller number of molecules, large networks of thermodynamic automata not unlike the TSMN might be achieved. Researchers from this same group [ 54 ] have recently demonstrated important steps in this direction in more complex photochemical systems, in which cell-like vesicles—“chemical protocells”—spontaneously assemble, collapse, move, and interact with each other while carrying internal chemistry unique to their history. The various evolutionary processes in these systems naturally integrate scales and sample diverse configurations.…”